Azo dyestuffs derived from amino-acylamino-salicyl-diphenylsulphones



Patented Mar. 11, 1930 UNITED STATES PATENT OFFICE WILHELM NEELMEIER, OFLEVERKUSEN, AND WINFRID HENTRICH, OF WIESDORF, NEARCOLOGNE-ON-THE-RHINE, GERMANY, ASSIGNORS TO GENERAL ANILINE WORKS, INC.,OF NEW YORK, N. Y., A CORPORATION OF DELAWARE AZO DYESTUFFS DERIVED FROMAMINO-ACYLAMINO-SALICYL-DIPHE'NYLSULPHONES No Drawing. Application filedNovember 5, 1926, Serial No. 146,558, and in Germany January 13, 1925.

We have shown in our co-pending application Serial No. 80,069, filedJanuary 8, 1926, that very valuable mordant dyestuffs are obtainedwhenone uses in their production diazo-compounds obtained from such aminoderivatives of diphenylsulphones,

their homologues or substitution products, as contain a hydroxyl and acarboxyl group, in ortho position to each other, in the nucleus whichdoes not contain the amino group.

We have now found that similar, improved dyestuffs are obtained when theabove described diphenylsulphone compounds contain in addition, in thenucleus containing the amino group, a second amino group which might befurther acidylated, that is to say, one of the hydrogens of the aminogroup replaced by an acidyl radicle. The general formula of thesediphenylsulphone compounds can be represented as follows:

n so on NHR, C' 00011 in which R stands for hydrogen or an acidyl grouand the hydroxyl and carboxyl oups 3o stan in ortho position to eachother; or the sake of convenience these sulphones might be calleddiaminophenyl-salicyl sulphones.

The process of producing our novel dyestufls comprises diazotizing adiaminophenyl-salicyl sulphone, coupling the so obtained diazo compoundwith any desired coupling compound and eventually splitting of! theacidyl group. Their general constitution can be represented by theformula:

in which R stands again for hydrogen or an acidyl group, R stands for aresidue of a coupling compound, and the hydroxyl and carboxyl groupsstand in ortho position to each other.

As coupling compounds there may be used any of the well knownazo-dyestuif coupling components, but we have found that very valuabledyestufls are obtained by the use as coupling compounds ofamino-naphthalene sulphonic acids or amino-naphthol sulphonic acids. Thedyestuffs so prepared dye chrome mordanted wool red to violet shades.The same shades are obtained when wool dyed with the said dyestuffs issubjected to an after-chroming treatment. The dyestuffs also aresuitable for use in cotton printing, especially since they are very fastto soaping and to fulling. Due to the external position of the groupproducing the mordanting properties, these dyestuffs possess theadditional advantage that their dyeings with chroming vary in shadelittle if at all from the direct dyeings.

Our invention is illustrated by the followin examples, the parts beingby weight.

mamp e 1.-350 parts 2-amino-5-acetylamino -4 hydroxydiphenylsulphone 3-carboxylic acid (obtained by condensing 1 molecular proportionquinone-di-imine with 1 molecular proportion salicylsulfinic acid andacetylating one only of the two amino groups of the2-fi-diamino-4-hydroxydiphenylsulphone-3'-carboxylic acid obtainedprimarily) are dissolved at about 40 C. in the requisite amount ofaqueous ammonia. 69 parts sodium nitrite are added to the so obtainedsolution: it is cooled to about 5 C. and excess 20% hydrochloric acidadded, the yellowish diazo-compound separates. This is combined at about5 C. with a neutral aqueous solution of 259 parts2-methylaminonaphthalene-7-sulphonate of sodium. 'The coupling proceedsrapidly, the mineral acidity is neutralized by the addition of sodiumacetate and the finished dyestufi is salted out and isolated in theusual manner. After- Hogs N-H IE- 1 COOH SO OH In coupling in acidsolution diazotized 2- amino 5 -acetylamino-4-hydroxy-diphenylsu1phone-3-carboxylic acid with 2-amino-8- naphthol-G-sulfonic acid aproduct of the probable constitution HOsS N 00011 solfion is obtained.After-chromedldyeings obtained therefrom possess a clear, very bluishred shade.

.The dyestuff of the following formula:

HOzS

H I? bi COOH is obtained by splitting off the acetyl group from theabove-described dyestuif. Wool dyed with this-dye'stufi and afterwardssubected to after-chroming shows a violet coloration.

Substitution of a benzoyl or a phthaloyl group for the acetyl group inthe above dyestuffs produces still more bluish dyeings. Similar shadesare also obtained by using as first component the diaz'o compoundobtained from 2-amino-5 acetylamino--methoxy 4' hydroxy-diphenylsulphone- 3'-carboxylic acid.

We claim: 1. As new products the mordant dyestuffs of the generalformula:

in which R stands for hydrogen or an acidyl group, R stands for aresidue of a coupling compound, and the hydroxyl and carboxyl groupsstand in ortho position to each other. 2. As new products the mordantdyestuffs of the formula Rz-N NHR in which R stands for a residue of acoupling compound of the naphthalene series and It stands for an acidylgroup. i

3. As a new product the mordant dyestufl which in the form of its freeacidvhas the formula which dyes wool after chromed beautiful red shadesof excellent fastness to light, washing and fulling. p

4. As new products the mordant dyestuffs of the general formula:

NILE

wherein R stands for an acidyl group and R for the residue of anaphthalene sulphonic acid compound being substituted in at least oneortho-position tovthe azo group by an amino group which may besubstituted.

In testimony whereof, We aflix our signatures.

' WILHELM NEELM'EIER.

WINFRID HENTRIOH.

